Ionic perfluorovinyl compounds and their uses as components of ionic conductors of the polymer type, of selective membranes or of catalysts

ABSTRACT

Ionic perfluorovinyl compounds and their uses as components of ionic conductors of the polymer type, of selective membranes or of catalysts. The compounds comprise at least one perfluorovinyl group and at least one group chosen from —O or one of the groups C≡N, —C(C≡N) 2 , —NSO 2 R or —C[SO 2 R] 2  or a pentacyclic group comprising at least one N, C—C≡N, CR, CCOR or CSO 2 R group. The compounds and/or their polymers are of use in the preparation of ionically conducting materials, electrolytes and selective membranes.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The subject matter of the present invention is ionicperfluorovinyl compounds, the polymers obtained from these compounds andtheir applications.

[0003] 2. Description of the Prior Art

[0004] Polyelectrolytes of polyanion type incorporating functionalgroups of sulfonate or carboxylate type are known as ion-exchange resins(polyacrylic acid, polystyrenesulfonic acid optionally crosslinked withdivinylbenzene). These polyelectrolytes are dissociated solely in thepresence of water or of highly polar protic solvents, such aspolyalcohols, for example ethylene glycol or glycerol. The correspondingacid groups (carboxylic or sulfonic acids) do not exhibit markedcatalytic properties due to the absence of swelling of the resin and thestrong association of ion pairs. In the form of membranes, thesepolymers only have a mediocre stability under the operating conditionsof a hydrogen-air fuel cell; in particular, they are rapidly degraded byoxidizing species present on the oxygen electrode side. Likewise, thesepolymers cannot be used in membrane processes, such as thechlorine-sodium hydroxide electrochemical process.

[0005] Furthermore, perfluorinated membranes (Nafion®) carrying sulfonicgroups are known which exhibit good chemical stability under theoperating conditions of a fuel cell and for the chlorine-sodiumhydroxide process. These materials are copolymers of tetrafluoroethylene(TFE) and of a comonomer carrying sulfonyl functional groups. However,the impossibility of crosslinking these polymers requires that thedensity of ionic groups be kept low, in order to prevent the resultingpolymers from being excessively soluble or swollen by water, resultingin a mediocre mechanical strength and a relatively limited conductivity.Furthermore, these membranes exhibit a high permeability to gases(oxygen and hydrogen) and to certain solvents, such as methanol, whichis harmful to the energy efficiency of fuel cells, more especially thoseof methanolair type (“crossover”). Furthermore, although the sulfonategroups attached to perfluorinated groups are partially dissociated inaprotic solvents and although the solvating polymers are particularlyadvantageous for secondary batteries in which the reactions at theelectrodes involve lithium ions, the conductivity of the gels obtainedby swelling Nafion® membranes with aprotic solvents, alone or as amixture, and the conductivity of the mixtures of these polyelectrolyteswith polyethers based on ethylene oxide remain too low. Furthermore, thesignificant fraction of perfluorinated segments —CF₂CF₂— resulting fromthe TFE comonomer makes these compounds sensitive to reduction atpotentials close to those of the negative electrode, resulting in thepolymer being destroyed. Moreover, the chemistry of these polymers iscomplex and expensive, and the yield in the manufacture of the monomerof perfluorovinyl ether type:

CF₂═CF—O—[CF₂CF(CF₃)]_(p)—O—CF₂CF₂SO₂F, 0≦p≦5

[0006] by thermal cracking of perfluoropolyethers-acid fluoride obtainedby addition of CF₃CF═CF₂ to isomerized sultones is low and limits theuse of these materials.

[0007] Polymers which comprise anions attached to the backbone of thepolymer and which are optionally plasticized or gelled by a solvent ofpolar type are of great advantage in electrochemical systems, such asprimary or secondary batteries, supercapacitors or systems formodulating light (electrochromic windows). Such polymers are mainlyderivatives of ethylene oxide, of acrylonitrile, of polyesters of alkylor oxaalkyl acrylate or methacrylate type, or of vinylidene fluoride.The production of monomers carrying highly delocalized anionicfunctional groups which can be incorporated, either by copolymerizationor by cocrosslinking or alternatively by mixing polymers, inmacromolecular materials such as those used in the electrochemicalsystems described above is therefore highly advantageous. The ionicmonomers described above as components of membranes of Nafion® typecannot be suitable for this use because the high fraction ofperfluorinated segments necessary in order to obtain the maximumconductivity in aprotic media (=1M.1⁻¹) corresponds to a decreaseddielectric constant in the vicinity of the ions and to an increasedsegmental stiffness, which are unfavorable to the movement of the ions.Moreover, the sulfonate groups are insufficiently dissociated incomparison with the salts of anions delocalized from nitrogenous centersor from carbon, such as, for example, the anion corresponding to theformula (R_(F)SO₂)X(SO₂R′_(F))⁻, in which X is N, C—R or C—SO₂R″_(F),R_(F), R′_(F) and R″_(F) are chosen from fluorine and fluorinatedmonovalent groups, or else R_(F) and R′_(F) form the components of adivalent ring, and R═H or any monovalent organic radical.

[0008] W. Navarrini et al. (U.S. Pat. No. 5,103,049) disclose methodsfor the preparation of R_(f)—CF═CF—SO₂F compounds in which R_(f) is F ora perfluoroalkyl group comprising 1 to 9 carbon atoms. Among thesecompounds, only CF₂═CFSO₂F is capable of acting as basis for monomerswhich can polymerize without steric constraints. However, this materialhas been shown to be too reactive to act as a precursor for monomersalts and anions, because the nucleophilic addition to the C═C doublebond, which is depleted in electrons both by the fluorine atoms and bythe —SO₂F group, generally takes place more rapidly than thesubstitution of the fluorine of the SO₂F group, thus preventing accessto ionic monomers or to precursors of ionic compounds (“Studies of theChemistry of Perfluorovinylsulfonyl Fluoride”, Forohar Farhad, ClemsonUniversity, Thesis 1990 UMI 9115049). In particular, the methods for thepreparation of anionic compounds used with RFSO₂F compounds cannot beapplied to the compound CF₂═CF—SO₂F. A process which consists inattaching a perfluorovinyl group to a phenyl nucleus carrying an SO₂Fgroup has been provided by C. Stone et al. (WO/96/39379); however, inthis case too, it is not possible to convert the CF₂═CF—C₆H₄SO₂Fmolecule to an anionic monomer because of the sensitivity of the CF₂═CF—group, which is more reactive than —SO₂F with respect to bases of OH— orNH₃ type.

[0009] Another process for the preparation of monomers of the TFE typecomprising an anion has been provided by D. Desmarteau et al. (U.S. Pat.No. 5,463,005). It consists in preparing a compound comprising aperfluorovinyl group and an SO₂F group, in protecting the perfluorovinylgroup, for example by addition of Cl₂, in converting the SO₂F group toan ionic group and in then deprotecting the perfluorovinyl group. Such aprocess is nevertheless lengthy and expensive and the polymers obtainedfrom said monomers exhibit the same disadvantages as the polymers ofNafion® type, resulting from the low content of SO₃ ⁻ or sulfonimideions in the absence of crosslinking.

[0010] The aim of the present invention is to provide a novel family ofionic compounds, which compounds exhibit extensive delocalization of thenegative charge and good activity in polymerization or incopolymerization and allow the preparation of macromolecules possessingdissociated and stable ionic functional groups, and a process for thepreparation of these compounds from fluorinated derivatives which arecommercially available at low cost, for example hydrofluorocarbons orhalocarbons.

[0011] For this reason, the subject matter of the present invention isionic monomer compounds, the homopolymers and the copolymers obtainedfrom these compounds, their applications and a process for theirpreparation.

SUMMARY OF THE INVENTION

[0012] A compound according to the invention is an ionic compound inwhich the negative charge is highly delocalized and which corresponds tothe formula

[CF₂═CF-A⁻]_(m)M^(m+), in which:

[0013] M^(m+) is a proton or a metal cation having the valency m chosenfrom the ions of alkali metals, of alkaline earth metals, of transitionmetals or of rare earth metals or an organic onium cation or anorganometallic cation, 1≦m≦3;

[0014] A⁻ represents an anionic group corresponding to one of thefollowing formulae:

[—(CF₂)_(n)—SO₂Z]⁻  (I)

[—(O)_(n′)-Φ-SO₂Z]⁻  (II)

[0015] n and n′ represent 0 or 1;

[0016] Φ represents a condensed or noncondensed aromatic group, whichmay or may not carry one or more substituents and which may or may notcomprise heteroatoms, or a polyhalogenated group—C₆H(_(4-x-y))F_(x)Cl_(y)— (1≦x+y≦4);

[0017] Z represents —O or one of the —NC≡N, —C(C≡N)₂, —NSO₂R or C[SO₂R]₂groups, Z being other than −0 when n or n′ are zero;

[0018] D represents a single bond, an oxygen atom, a sulfur atom, a —CO—carbonyl group or an —SO₂— sulfonyl group;

[0019] the groups X′ to X⁴, hereinafter denoted by X′, represent N,CC—N, CR, CCOR or CSO₂R, it being understood that, in a pentacyclicgroup, the X¹ groups can be identical or different;

[0020] R represents Y, YO—, YS—, Y₂N—, F, R_(F)=C_(q)F_(2q+1)(preferably 0≦q≦12), CF₂═CF—, CF₂═CFCF₂— or CF₂═CF—O—, it beingunderstood that, if 2 R substituents are present on the same group, theycan be identical or different;

[0021] Y represents H or a monovalent organic radical having from 1 to16 carbon atoms chosen from alkyl, alkenyl, oxaalkyl, oxaalkenyl,azaalkyl, azaalkenyl, aryl or alkylaryl radicals or from the radicalsobtained from the abovementioned radicals by substitution, in the chainsand/or the aromatic part, by heteroatoms, such as halogens, oxygen,nitrogen, sulfur or phosphorus, it being understood that, if sulfur orphosphorus are present, they can optionally be bonded to substitutednitrogen or oxygen atoms, or else Y is a repeat unit of a polymericbackbone.

[0022] The divalent radical Φ can be a phenyl C₆H₄ corresponding to theortho, meta and para positions of substitution. It can be an aromaticgroup, a phenyl which is substituted and/or comprising condensed nucleiwhich may or may not comprise heteroatoms. Φ is preferably a halogenatedphenyl group or a phenyl group carrying 1 to 2 CF₃ substituents or apyridyl nucleus.

[0023] When M^(m+) is a metal cation, it can be an alkali metal (inparticular K⁺ or Li⁺), an alkaline earth metal (in particular Mg⁺⁺, Ca⁺⁺or Ba⁺⁺), a transition metal (in particular Cu⁺⁺, Zn⁺⁺ or Fe⁺⁺) or arare earth metal (in particular Re⁺⁺⁺).

[0024] When M^(m+) is an onium cation, it can be chosen from ammoniumions [N(Y^(j))₄]⁺, amidinium ions RC[N(Y^(j))₂]₂ ⁺, guanidinium ionsC[N(Y^(j))₂]₃ ⁺, pyridinium ions [C₅N(Y^(j))₆]⁺, imidazolium ionsC₃N₂(Y^(j))₅ ⁺, imidazolinium ions C₃N₂(Y^(j))₇ ⁺, triazolium ionsC₂N₃(Y^(j))₄ ⁺, carbonium ions C₅(Y^(j))₅C⁺, NO⁺ (nitrosyl) or NO₂ ⁺ions, sulfonium ions [S(Y^(j))₃]⁺, phosphonium ions [P(Y^(j))₄]⁺ andiodonium ions [1(Y^(j))₂]⁺. In the various abovementioned onium ions,the Yi substituents of the same cation can be identical or different.They represent one of the substituents indicated above for Y.

[0025] When M^(m+) is an organometallic cation, it can be chosen frommetalloceniums. It can also be chosen from metal cations coordinated byatoms, such as O, S, Se, N, P or As, carried by organic molecules, thesecations optionally forming part of a polymeric backbone. M^(m+) can alsobe a cation derived from the alkyl groups defined for Y above andlimited to those having from 1 to 10 carbon atoms, for example atrialkylsilyl, trialkylgermanyl or trialkylstannyl derivative; in thiscase, M is connected to [CF₂═CF-A] by a very labile covalent bond andthe compound behaves as a salt. The Mm+cation can also be the repeatunit of a conjugated polymer in cationic oxidized form.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] Mention may be made, among the compounds of the presentinvention, of the following monofunctional monomers:{[CF₂═CF—SO₂NCN]⁻}_(m)M^(m+), {[CF₂═CF—SO₂C(CN)₂]⁻}_(m)M^(m+),{[CF₂═CFCF₂—SO₂NCN]⁻}_(m)M^(m+), {[CF₂═CFCF₂SO₂C(CN)₂]⁻}_(m)M^(m+),{[CF₂═CF—SO₂NCN]⁻}_(m)M^(m+), {[CF₂═CF-ΦSO₂C(CN)₂]⁻}_(m)M^(m+),{[CF₂═CF-ΦSO₂NSO₂CF₃]⁻}_(m)M^(m+), {[CF₂═CF-ΦSO₂C(SO₂CF₃)₂]1}_(m)M^(m+),{[CF₂═CF-ΦSO₂CH(SO₂CF₃)]⁻}_(m)M^(m+),

[0027] Mention may also be made of the following di- and trifunctionalmonomers {[(CF₂═CFCF₂—SO₂)₂N]⁻}_(m)M^(m+),{[(CF₂═CFSO₂)₂CH]⁻}_(m)M^(m+), {[(CF₂═CFCF₂—SO₂)₂CH]⁻}mMM+,{[(CF₂═CF—SO₂)₃C]⁻}_(m)M^(m+), {[(CF₂═CFCF₂SO₂)₃C]⁻}_(m)M^(m+),{[(CF₂═CF-ΦSO₂)₂N]⁻}_(m)M^(m+″), {[(CF₂═CF—O-ΦSO₂)₂N]⁻}_(m)M^(m+),{[(CF₂═CF-ΦSO₂)₂CH]⁻}_(m)M^(m+), {[(CF₂═CF—O-ΦSO₂)₂CH]⁻}_(m)M^(m+),{[(CF₂═CF-ΦSO₂)₃C]⁻}_(m)M^(m+), {[(CF₂═CF—O-ΦSO₂)₂CH]⁻}_(m)M^(m+),{[(CF₂═CF-ΦSO₂)₃C]⁻}_(m)M^(m+), {[(CF₂═CF—O-ΦSO₂)₃C]⁻}_(m)M^(m+),{[(CF₂═CF—)₂C₆H₃SO₃]⁻}_(m)M^(m+),{[3,5-(CF₂═CF—)₂C₆H₃SO₂NSO₂CF₃]⁻}M^(m+)

[0028] Preference is very particularly given, among the abovementionedcompounds, to those in which Φ is —C₆H₄—.

[0029] The ionic monomer compounds of the present invention can beprepared by various synthetic routes.

[0030] In a first embodiment, a compound comprising the perfluorovinylgroup is reacted with an ionic compound having an anionic part A¹, thestructure of which is analogous to that of the anionic part A of thedesired compound, and having from one to 3 leaving groups.

[0031] The subject matter of the invention is a process for thepreparation of an ionic monomer compound [CF₂═CF-A⁻]_(m)M^(m+) asdefined above in which an organometallic compound (OM1) is reacted instoichiometric proportions with an ionic compound (IC1) in the presenceof a catalyst, characterized in that:

[0032] the organometallic compound (OM1) corresponds to the formula

[CF₂═CF—(CF₂)_(n)]_(e)—E, in which:

[0033] E represents Li, MgL¹, ZnL¹, CdL¹, Cu, Mg, Zn, Cd, Hg or atrialkylsilyl, trialkylgermanyl or trialkylstannyl group;

[0034] n is 0 or 1;

[0035] e represents the valency of E;

[0036] L¹ represents a leaving group chosen from halogens,pseudohalogens, including sulfonates, radicals comprising imidazole or1,2,4-triazole rings and their homologs in which one or more carbonatoms carry substituents, including those in which the substituents forma ring (for example a benzotriazole), perfluoroalkylsulfonyloxy radicalsand arylsulfonyloxy radicals;

[0037] the ionic compound (IC1) corresponds to the formula

[(LA¹)⁻]_(m′)M′^(m′+) in which:

[0038] M′^(m′+) represents a proton or a metal cation having the valencym chosen from ions of alkali metals, of alkaline earth metals, oftransition metals or of rare earth metals, or an organic onium cation,or an organometallic cation, 1≦m≦3. M′ is chosen so as not to interferewith the formation reaction;

[0039] L has the same meaning as L¹, it being understood that the L andL¹ groups of the respective reactants used during a reaction can beidentical or different;

[0040] A¹ represents an anionic group corresponding to one of thefollowing formulae:

[—(CF₂)_(n)—SO₂Z¹]⁻

[—(O)_(n′)-ΦS₂Z¹]⁻

[0041] in which:

[0042] n and n′ represent 0 or 1;

[0043] D represents a single bond, an oxygen atom, a sulfur atom, a —CO—carbonyl group or an —SO₂— sulfonyl group;

[0044] Z¹ represents the —O oxygen (except if n or n′ are zero) or oneof the —NC≡N, —C(C≡N)₂, —NSO₂R¹ and —C[SO₂R¹]₂ groups;

[0045] the X′¹ to X′⁴ groups, hereinafter denoted by X′¹, represent N,C—C≡N, CR¹, CCOR¹ or CSO₂R¹, it being understood that, in a pentacyclicgroup, the X′¹ groups can be identical or different;

[0046] R¹ represents Y, YO—, YS—, Y₂N—, F, CF₂═CF—, CF₂═CFCF₂—,CF₂═CF—O— or R_(F)=C_(q)F_(2q+1) (0≦q≦12), or a leaving group chosenfrom halogens, pseudohalogens, including sulfonates, radicals comprisingimidazole or 1,2,4-triazole rings and their homologs,perfluoroalkylsulfonyloxy radicals and arylsulfonyloxy radicals, itbeing understood that, if two R¹ substituents are present on the samegroup, they can be identical or different and that at most two R¹substituents are leaving groups;

[0047] Y has the meaning given above.

[0048] When the M′ cation of the reactant used is different from the Mcation of the desired final compound, the compound obtained is modifiedby conventional cation-exchange techniques.

[0049] The preferred leaving groups L and L′ are F, Cl, Br, I, theimidazole radical, the trifluoromethanesulfonyloxy radical CF₃SO₃— andarylsulfonyloxy radicals.

[0050] Preference is very particularly given, for the ionic compounds(IC1), to the following anionic groups: [(FSO₂)NSO₂R_(F)]⁻,[(ClSO₂)NSO₂R_(F)]⁻, [(ImSO₂)NSO₂RF]⁻, [(FSO₂)₂N]⁻, [(CISO₂)₂N]⁻,[(ImSO₂)₂N]⁻, [(FSO₂)NCN]⁻, [(CISO₂)NCN]⁻, [(ImSO₂)NCN]⁻,[(FSO₂)C(R)SO₂R_(F)]⁻, [(ClSO₂)C(R)SO₂R_(F)]⁻, [(ImSO₂)C(R)SO₂R_(F)]⁻,[(FSO₂)₂CR]⁻, [(CISO₂)₂CR]⁻, [(ImSO₂)₂CR]⁻, [(FSO₂)C(CN)₂]⁻,[(ClSO₂)C(CN)₂], [(ImSO₂)C(CN)₂]⁻, [(FSO₂)₃C]⁻, [(ClSO₂)₃C]⁻,[(ImSO₂)₃C]⁻, [(ClΦSO₂)NSO₂R_(F)]⁻, [(BrΦSO₂)NSO₂R_(F)]⁻,[(IΦSO₂)NSO₂R_(F)]⁻, [(CF₃SO₃ΦSO₂)NSO₂R_(F)]⁻,[(CH₃ΦSO₃ΦSO₂)NSO₂R_(F)]⁻, [3,5-Br₂C₆H₃SO₃]1, [3,5-Br₂C₆H₃SO₂R_(F))]⁻,[3,5]₂C₆H₃SO₃]⁻, [3,5-I₂C₆H₃SO₂N(SO₂R_(F))]⁻, [(BrΦSO₂)NCN]⁻,[(IΦSO₂)NCN]⁻, [(CF₃SO₃ΦSO₂)NCN]⁻, [(CH₃ΦSO₃ΦSO₂)NCN]⁻,[(CH₃ΦSO₂)C(CN)₂]⁻, [(BrΦSO₂)C(CN)₂]⁻, [(IΦSO₂)C(CN)₂]⁻,[(CF₃SO₃ΦSO₂)C(CN)₂]⁻, [(CH₃ΦSO₃ΦSO₂)C(CN)]⁻, [(ClΦSO₂)N(SO_(2ΦCl)]) ⁻,[(BrΦSO₂)N(SO₂ΦBr)]⁻, [(IΦSO₂)N(SO₂Φ)]⁻, [(CF₃SO₃ΦSO₂)N(SO₂ΦSO₃CF₃)]⁻,[(CH₃ΦSO₃ΦSO₂)N(SO₂ΦSO₃ΦCH₃)]⁻, [(ClΦSO₂)₂C(SO₂R_(F))]⁻,[(BrΦSO₂)₂C(SO₂R_(F))]⁻, [(IΦSO₂)₂C(SO₂R_(F))]⁻,[(CF₃SO₃ΦSO₂)₂C(SO₂R_(F))]⁻, [(ClΦSO₂)C(SO₂R_(F))₂]⁻,[(BrΦSO₂)C(SO₂R_(F))₂], [(IΦSO₂)C(So₂R_(F))₂]⁻,[(CF₃SO₃ΦSO₂)C(SO₂R_(F))₂]⁻,[(CH₃ΦSO₃ΦSO₂)C(SO₂R_(F))₂]⁻,[BrΦC(So₂R_(F))₂]⁻,[3,5Br₂C₆H₃C(So₂R_(F))₂]⁻,

[0051] In the abovementioned anionic groups of the compounds (IC1), Rand RF have the meaning given above and preferably comprise from 0 to 10carbon atoms.

[0052] A compound (OM1) such as CF₂═CF—Li is prepared by reaction of astrong base B and of a lithiating agent R′—Li with1,1,1,2-tetrafluoroethane at low temperature, according to the reactionscheme:

[0053] CF₃—CH₂F+B CF₂═CHF+[BHF]

[0054] CF₂═CHF+R′Li

CF₂═CFLi++R′H

[0055] The compounds CF₂═CF-E in which E is other than Li can beobtained by ion exchange.

[0056] It is advantageous to use butyllithium both as strong base and aslithiating agent.

[0057] The compound CF₂═CFCF₂-E can be prepared from perfluoroallylfluorosulfate by simple nucleophilic substitution according to thefollowing reaction scheme:

[0058] KI is a particularly appropriate compound M⁺E³⁶⁴ ⁻.

[0059] The organometallic compounds (OM1) are more particularly chosenfrom: CF₂═CFLi, (CF₂═CF)_(2-x)Mg(Hal)_(x), (CF₂═CF)_(2-x)Zn(Hal)_(x),(CF₂═CR)_(2-x)Cd(Hal)_(x) (0≦x≦2); Hal=Cl, Br, I, pseudohalogen),(CF₂═CF)₃YAl(1Hal)_(y), (0≦y≦3); CF₂═CFCu, CF₂═CFSi(CH₃)₃,CF₂═CFSi(C₂H₅)₃, CF₂=CFSn(CH₃)₃, CF₂═CFSn(C₂H₅)₃, CF₂═CFSn(C₄H₉)₃,CF₂═CFCF₂CdBr, CF₂═CFCF₂Cu, CF₂═CFCF₂Zn(O₃SF), CF₂═CFCF₂Si(CH₃)₃ andCF₂═CFCF₂Si(C₂H₅)₃.

[0060] It is known to a person skilled in the art that the stability andthe processing conditions for halogenated organometallic compounds varyaccording to the nature of E; in particular, organolithium compounds areonly stable at temperatures of less than −60° C. and are habituallyprepared and used at the temperature of dry ice, whereas more covalentcompounds, such as silane derivatives, are stable even above roomtemperature.

[0061] The process is carried out in the presence of a catalyst chosenfrom derivatives of nickel or palladium coordinated with bases of amineor phosphine type. Mention may be made, by way of example, of nickelbis(2,2′-bipyridyl), nickel tetrakis(triphenylphosphine) and itssulfonated derivatives, palladium acetate,trisbenzylideneketonedipalladium, palladium tetrakis(triphenylphosphine)and its sulfonated derivatives, and the compounds obtained byreplacement of two triphenylphosphine molecules by [(C₆H₅)₂PCH₂]₂ or[(C₆H₅)₂PCH₂]₂CH₂. Nickel and palladium have catalytic properties forso-called Suzuki coupling reactions when their degree of oxidation isgreater than or equal to 0 and less than or equal to 2.

[0062] In another embodiment of the invention, an ionic monomer compound[CF₂═CF-A⁻]_(m)M^(m+) according to the invention is prepared by reactinga compound comprising a protected fluorovinyl groupCF₂L³CFL⁴—(CF₂)_(n)E¹ with a reactant [(L⁵)_(a)A²]_(m′)M′^(m′+) makingpossible the formation of the anionic group A and then the protectivegroups are removed by a chemical or electrochemical reduction or by adehydrohalogenation. M′ has the meaning indicated above. L³ and L⁴represent H or a halogen, just one among them optionally being H. E¹ hasthe meaning given above for E. L⁵ represents a leaving group having thesame definition as the leaving group L. “a” is the valency of theanionic group A². A² represents a group corresponding to one of thefollowing formulae [—(CF₂)_(n)SO₂Z²]⁻, [—(O)_(n′)-ΦSO₂Z²]⁻ or

[0063] in which:

[0064] n, n′, D and Φ have the meaning indicated above;

[0065] Z² represents the —O oxygen (except if n or n′ are zero) or oneof the groups —NC≡N, —C(C—N)₂, —NSO₂R² or —C[SO₂R²]₂;

[0066] the groups X″¹ to X″⁴, hereinafter denoted by X″¹, represent N,C—C≡N, CR², CCOR² or CSO₂R², it being understood that, in a pentacyclicgroup, the X″¹ groups can be identical or different;

[0067] R² represents —OH, —SH, Y, YO—, YS—, Y₂N—, F, CF₂═CF—,CF₂═CFCF₂—CF═CF—O— or R_(F)=C_(q)F_(2q+1) (0≦q≦12), it being understoodthat, if two R² substituents are present on the same group, they can beidentical or different and that at most two R² substituents represent—OH or —SH;

[0068] Y has the meaning given above.

[0069] Mention may be made, by way of example, of the followingreaction: (ClSO₂)₂NK+2CF₂Cl—CFClLi

(CF₂Cl—CFClSO₂)₂NK+2LiCl.

[0070] When the cation M′ of the reactant used is different from thecation M of the desired final compound, the compound obtained ismodified by conventional cation-exchange techniques. The greaterresistance of the compounds thus protected with respect to nucleophiles,in particular bases, makes it possible to carry out reactions onmolecules acting as intermediate in the preparation of the monomeranions, reactions which would be impossible if the ethylenic double bondwas unprotected. In particular, it is possible to form intermediates ofsulfamide or hydrazide type allowing the construction of anionicspecies.

[0071] For example, the anion derived by addition of chlorine totrifluoroacrylic acid can be converted to a triazole group via ahydrazide. The triazole anion, more dissociated than the carboxyl anion,is obtained according to the simplified scheme:

[0072] The starting fluorinated acrylic acid is easily prepared byreaction of CO₂ with an organometallic derivative, such as CF₂═CFLi,itself easily obtained by reaction of an alkyllithium with thecommercial compound 1,1,1,2tetrafluoroethane sold under the tradenameKlea®.

[0073] Similar reactions are possible with a compound comprising asulfurbased anionic group, such as a sulfonate. They make it possible toobtain, via a sulfamide, a compound comprising an anionic sulfonylimidegroup which is more dissociated than the sulfonate group, by thefollowing reaction stages:

[0074] sulfonate+chlorinating agent RSO₂Cl

[0075] RSO₂Cl+NH₃

RSO₂NH₂;

[0076] RSO₂NH₂+R′SO₂Cl

RSO₂N(H)SO₂R′

[0077] These reactions cannot be carried out if R═CF₂═CF. On the otherhand, the desired result is obtained if R═CF₂Cl—CFCl and, for example,R′=R or CF₃. The sulfonate is easily obtained by the followingreactions: CF₂Cl—CFClLi+ClSO₃Si(CH₃)₃

CF₂Cl—CFSO₃Li+ClSi(CH₃)₃.

[0078] A compound [CF₂L²-CFL³-(CF₂)_(n)]-E′, in particular CF₂ClCFClLi,can be obtained by reaction of the corresponding compound[CF₂═CF—(CF₂)_(n)]-E′ with a compound L²L³ at a temperature of between−80° C. and 110° C., for example in the Trapp mixture (THF/ether/pentanecomposition). Mention may be made, among the compounds L²L³ which areeasily added to the perfluorovinyl double bond, of FC1, Cl₂, ClBr, Br₂,ICI, IBr, 12, (SCN)₂, HCl, HBr and HI. The lithium compounds (OM2) canact as the basis for the preparation of other organometallic compounds,such as silicon or zinc derivatives, by exchange.

[0079] The (L²)/(L³) and L²H pairs are preferably chosen from Cl₂, Br₂,FCI, FBr, BrCl, ICI, HF, HCl and HBr, Cl₂ and HCl being particularlypreferred.

[0080] The L²L³ groups are easily removed by reduction or bydehydrohalogenation. The reducing agent is advantageously chosen fromzinc, the copper-zinc couple, Ti³+, V²+, Cr³⁺ or Sm²+salts, andtetrakis(dimethylaminoethylene) {[(CH₃)₂N]₂C=}2. An electrochemicalreduction can also be carried out, directly or via the preceding metalsacting as mediators. The dehydrohalogenating agents are chosen fromstrong bases and are known to a person skilled in the art. Mention mayin particular be made of NaH [optionally used in the presence ofphosphorus-comprising bases of phosphazene P1-P4 type (Fluka AG, Basle,Catalog No. 79408, 79412, 79417, 79421, 422 79432)], (CH₃)₃CONa,(CH₃)₃COK, LDA (lithium diisopropylamide), [(CH₃)₂CH]₂NLi, orhexaalkyldisilazane derivatives, in particular [(CH₃)₃Si]₂NLi,[(CH₃)₃Si]₂NNa and [(CH₃)₃Si]₂NK.

[0081] In another embodiment, an ionic compound having an anionic partA³, the structure of which is analogous to that of the anionic part A ofthe desired compound, and having from one to 3 hydroxyl or thiol groupsis reacted with a compound comprising the perfluorovinyl group.

[0082] The subject matter of the invention is a process for thepreparation of an ionic monomer compound [CF₂═CF-A⁻]_(m)M^(m+) asdefined above, characterized in that a compound CF₂═CFL², in which L²represents Cl, Br or F, is reacted in stoichiometric proportions with anionic compound (IC2) [(HQA³)-]_(m′)(M′)_(m′+) and in that the additionproduct obtained is treated with a strong base B.

[0083] The reaction scheme is as follows: CF₂═CFL²+(HQA³)-HCF₂—CFL²-Q-A³ HCF₂—CFL²-Q-A³+Base CF₂═CF-Q-A³+BaseHL

[0084] The cationic part (M′)_(m′+) has the meaning given above, alkalimetal cations being preferred.

[0085] The anionic part (HQA³)- is such that:

[0086] * Q represents O or S;

[0087] * A³ represents an anionic group corresponding to one of thefollowing formulae: [—(CF₂)_(n)—SO2Z³][-ΦSO₂Z³]

[0088] in which:

[0089] n and n′ have the meaning indicated above;

[0090] Z³ represents the —O oxygen (except if n is zero) or one of thegroups —NC≡N, —C(C≡N)₂, —NSO₂R³ or —C[SO₂R³]₂;

[0091] the groups X″ to X″⁴, hereinafter denoted by X″¹, represent N,C—C—N, CR³, CCOR³ or CSO₂R³, it being understood that, in a pentacyclicgroup, the X″¹ groups can be identical or different;

[0092] R³ represents HO—, HS—, Y, YO—, YS—, Y₂N—, F, CF₂═CF—,CF₂═CFCF₂—, CF₂═CF—O— or R_(F)=C_(q)F2q+1 (0≦q≦12), it being understoodthat, if two R³ substituents are present on the same group, they can beidentical or different and that at most two R³ substituents are —OH or—SH groups;

[0093] Y is as defined above.

[0094] The strong base B can be in particular NaH [optionally used inthe presence of phosphorus-comprising bases of phosphazene P1-P4 type(Fluka AG, Basle, Catalog No. 79408, 79412, 79417, 79421, 422 79432)],(CH₃)₃CONa, (CH₃)₃COK, LDA (lithium diisopropylamide), [(CH₃)₂CH]₂NLi,or hexaalkyldisilazane derivatives, in particular [(CH₃)₃Si]₂NLi,[(CH₃)₃Si]₂NNa and [(CH₃)₃Si]₂NK. Potassium t-butoxide is particularlyappropriate.

[0095] When the ionic compound (IC2) comprises a thiol, it is possibleto convert the sulfide of the anion [HCF₂—CFL²SA]- of the intermediateproduct obtained to the sulfone by oxidation. The electro-withdrawingpower of the sulfone contributes to decreasing the basicity of thecorresponding anion [HCF₂CFL²-SO₂-A]⁻ and it is then possible to removeL 2H under mild conditions, for example in the presence of a tertiarynitrogenous base.

[0096] The preferred compounds (IC2) are those which comprise one of thefollowing anions: [{HO-(Φ)SO₂}N(SO₂R_(F))]⁻, [{HS-((Φ)SO₂}N(SO₂R_(F))]⁻,[{HO(Φ)SO₂}NCN]⁻, [{HS(Φ)SO₂}NCN]⁻, [{HO(Φ)SO₂}C(CN)₂]⁻,[{HS(Φ)SO₂}C(CN)₂]⁻, [{HO(Φ)SO₂}N{SO₂(Φ)OH}]⁻, [{HS(Φ)SO₂}N(Φ)SH]⁻,[{HO(Φ)SO₂}₂C(R)]⁻, [{HO(Φ)SO₂}₂C(SO₂R)]⁻, [{HO(Φ)SO₂}₂C(So₂R_(F))]⁻,[{HO(Φ)SO₂}C(SO₂R_(F))₂]⁻, [{HS(Φ)SO₂}₂C(R)]⁻, [{HS(Φ)SO₂}₂C(SO₂R)]⁻,[{HS(Φ)SO₂}₂C(So₂R_(F))]⁻, [{HS(Φ)SO₂}C(So₂R_(F))₂]⁻, [3,5-(HO)₂—C₆H₃SO₃]⁻, [(3,5-(HO)₂—C₆H₃SO₂)N(SO₂R_(F))]⁻,[3,5-(HO)₂C₆H₃C(SO₂R_(F))]⁻, [{HO-(Φ)SO₂}₂C(So₂R_(F))]⁻,[{HS-(Φ)SO₂}₂C(So₂R_(F))]⁻,

[0097] In another embodiment, the compounds [CF₂═CF-A⁻]_(m)M^(m+) areprepared by a process, characterized in that it consists in reacting acompound L⁶CF₂CF₂L⁶ with an ionic compound [(HQA³)⁻]_(m′)M′^(m′+) instoichiometric proportions and in reducing the substitution compoundobtained, either chemically or electrochemically. The compound[(HQA³)⁻]_(m′)M′^(m′+) is as defined above. L⁶ represents a leavinggroup chosen from halogens, pseudohalogens and sulfonates. Halogens areparticularly preferred.

[0098] The substitution compounds obtained are subjected to a chemicalreduction or an electrochemical reduction in order to remove the L⁶leaving groups. The reduction can be catalyzed by zinc, the copper-zinccouple, Ti3+, V²+, Cr³⁺ or Sm²+salts, andtetrakis(dimethylaminoethylene) {[(CH₃)₂N]₂C=}₂. An electrochemicalreduction can be carried out, directly or via the preceding metalsacting as mediators.

[0099] The ionic compounds of the present invention, all of whichcomprise at least one CF₂═CF— group, can be polymerized by the radicalroute. The polymerization can be carried out in solution or in emulsionwith conventional radical initiators, such as peroxides, azo compounds,persulfates, photoinitiators of benzoin type or others. During thepreparation of crosslinked materials, the molecular mass between networknodes is not necessarily very high, which constitutes a significantadvantage with respect to materials of the Nafion® type.

[0100] A polymer according to the present invention is composed of apolyanionic part with which are associated cations in a numbersufficient to ensure the electronic neutrality of the polymer, thepolyanionic part being composed of repeat units:

[0101] in which A has the meaning given above in the definition of themonomer compounds of the present invention.

[0102] A polymer of the invention can also be composed of repeat units

[0103] Such a polymer is obtained by polymerization of a difunctionalcompound according to the invention in which the anionic group A -itself comprises a perfluorovinyl radical.

[0104] Such a compound [(CF₂═CF)₂-A′⁻]_(m)M^(m+) in which M has themeaning given above and A′ represents an anion corresponding to one ofthe formulae (I), (II) or (III) mentioned above in which a Z or X¹substituent comprises a perfluorovinyl radical. In this case, twoperfluorovinyl radicals form a ring comprising 4 carbons which isconnected to an analogous ring via the anionic part A′ in order to forma linear polymer.

[0105] The polymerization can be carried out starting from only thecompounds of the invention and a homopolymer is obtained in which eachof the repeat units carries an ionic group.

[0106] When the polymerization is carried out in the presence of acomonomer, it is possible to limit the amount of ionic groups on thecopolymer.

[0107] The polymerization of monofunctional monomers makes it possibleto obtain linear polymers. The polymerization of di- or trifunctionalmonomers, in which the anionic group A itself comprises one or twoadditional CF₂═CFgroups, makes it possible to obtain crosslinkedmacromolecular materials. In this case also, a copolymerization with acomonomer not carrying ionic groups makes it possible to adjust thenumber of functional groups introduced.

[0108] Generally, when the compounds of the present invention arepolymerized in the presence of a comonomer, the choice of the monomer,of the comonomer and of the number of polymerizable groups on themonomer and the comonomer makes it possible to adjust the properties ofthe macromolecular materials obtained according to the use which isanticipated for them.

[0109] The ionic compounds of the present invention comprise at leastone ionophoric group. They can thus be used for the preparation of ionconducting materials. The polymers obtained from the monomer compoundsof the invention, which have the property of polymerizing or ofcopolymerizing, comprise repeat units carrying an ionophoric group andcan thus also be used for the preparation of ion conducting materials,with the advantage of having an immobile anionic charge. An ionconducting material constituted by an ionic monomer compound in solutionin a solvent and an ion conducting material comprising a polymerobtained by polymerization of a monomer compound of the presentinvention consequently constitute further subject matters of the presentinvention.

[0110] The ion conducting materials of the present invention can be usedfor the preparation of the electrolyte or as binder of the electrodes ofenergy storage systems, such as primary or secondary batteries, fuelcells, in supercapacitors, in systems for modulating light transmission(electrochromic systems, electroluminescent diodes) or in sensors. Anelectrolyte obtained from a compound according to the invention can be aliquid electrolyte, a solid electrolyte or a gel electrolyte.

[0111] A plasticized electrolyte or an electrolyte in the gel formaccording to the invention can be composed of a mixture of at least onepolar solvent, of an ionic monomer compound of the invention and of apolar polymer. It can also be composed of at least one polar solvent anda polymer or copolymer obtained by polymerization of a monofunctionalcompound according to the present invention.

[0112] A solid electrolyte according to the invention comprises either acopolymer of at least one compound according to the invention and of oneor more precursors of solvating polyethers or a macromolecular materialobtained by cocrosslinking of at least one compound according to theinvention and of a solvating polyether carrying reactive functionalgroups capable of reacting with the perfluorovinyl group of thecompounds of the invention. In another embodiment, a solid electrolytecan comprise a mixture of a polyether and of a homopolymer or of acopolymer obtained from at least one compound of the invention carryingionic groups, it being possible for said mixture optionally to becrosslinked in order to form an interpenetrating network. In some cases,it can be advantageous to plasticize the macromolecular material byaddition of a polar solvent which is compatible with the etherfunctional groups. Depending on the amount of polar solvent added, theelectrolyte will be a plasticized solid electrolyte or a gelelectrolyte. The polar solvent is chosen, for example, from linearethers and cyclic ethers, esters, nitrites, nitro derivatives, amides,sulfones, alkylsulfamides and partially halogenated hydrocarbons.

[0113] An electrolyte can also be composed of a mixture of a homopolymeror of a copolymer of polar monomers (including a polyether) and of ahomopolymer or of a copolymer of ionic compounds of the presentinvention. The two mixed polymers can optionally be crosslinked to forman interpenetrating network and be plasticized by a polar liquid.

[0114] An electrolyte generally comprises a solvent (liquid, solid orgel) and at least one salt. When, in accordance with the presentinvention, an electrolyte comprises a macromolecular material obtainedfrom the compounds of the invention, the repeat units comprise ionicgroups which can completely or partially replace the salt conventionallyadded to a polymer solvent in order to constitute a polymer electrolyte.Polymers derived fromtrifluorovinylsulfonyl(trifluoromethylsulfonyl)imide and those derivedfrom trifluorovinylphenylsulfonyl(trifluoromethylsulfonyl)imide areparticularly advantageous for the preparation of electrolytes. Anelectrolyte obtained from a polymer according to the invention, in whichthe anions are at least partly immobilized on a polymer chain, has amainly cationic mobility, the effect of which is to greatly improve theoperation of electrochemical systems. In addition, a compound of theinvention can be used as salt added to a liquid or polymer electrolyte.

[0115] Use is preferably made, for the preparation of macromolecularmaterials of use as electrolyte, of compounds according to the inventionin which the cation is an alkali metal cation. Lithium and potassium areparticularly preferred. The more suitable anions are the mono- ordifunctional imides CF₂═CFSO₂NSO₂CF₃— or [CF₂═CFSO₂]₂N— orCF₂═CFC₆H₄SO₂NSO₂CF₃ ⁻.

[0116] When an electrolyte according to the present invention is used inan energy storage system, such as a primary battery or a secondarybattery, it is advantageous to use, as negative electrode, an electrodecomposed of metallic lithium or one of its alloys, optionally in theform of a nanometric dispersion in lithium oxide, or double nitrides oflithium and of a transition metal, or oxides of low potential having thegeneral formula Li_(4−x+y)Ti_(5+x)O₂ (0≦x≦1, 0≦y≦3), or carbon andcarbonaceous products resulting from the pyrolysis of organic materials.The positive electrode will advantageously be chosen from vanadiumoxides VOx (2≦x≦2.5), LiV₃O₈ or Li_(y)N_(1-x)Co_(x)O₂ (0≦x≦1; 0≦y≦1),manganese spinels Li_(y)Mn_(1−x)M_(x)O₂ (M=Cr, Al, V, Ni, 0≦x≦0.5;0≦y≦2), organic polydisulfides, FeS, FeS₂, iron sulfate Fe₂(SO₄)₃, ironand lithium phosphates and iron and lithium phosphosilicates with anolivine structure or analogous phosphosilicates in which the iron isreplaced by manganese, and sulfophosphates with a Nasicon structureLi_(x)Fe₂S_(1−x)P_(x)O₄. The abovementioned compounds may be used aloneor as a mixture.

[0117] When an electrolyte according to the present invention is used ina system for modulating light, such as an electrochromic system, use ispreferably made of an electrode material chosen from WO₃, MoO₃, iridiumoxyhydroxide IrO_(x)H_(y), 2≦x≦3; 0≦y≦3), Prussian blue, viologencompounds and their polymers, and aromatic polyimides.

[0118] When an ionically conducting material of the present invention isused as electrolyte in an energy storage system, such as asupercapacitor, use is preferably made of an electrode materialcomprising a carbon with a high specific surface or an electrodecomprising a redox polymer.

[0119] The monomer compounds of the present invention can be used forthe doping of polymers for the purpose of conferring an improvedelectronic conduction on them. The polymers concerned are essentiallypolyacetylenes, polyphenylenes, polypyrroles, polythiophenes,polyanilines, polyquinolines, which may or may not be substituted, andpolymers in which the aromatic units are separated by the vinylene unit—CH═CH—. The doping process consists in partially oxidizing the polymerin order to create carbocations, the charge of which is compensated forby the anions of the compounds of the invention. This doping can becarried out chemically or electrochemically, optionally simultaneouslywith the formation of the polymer. For this specific application, thechoice is preferably made of the compounds of the invention carrying ahighly delocalized charge, in particular compounds in which Z is—C(C≡N)₂, —NSO₂R or —C(SO₂R)₂, which confer thermal and mechanicalstability properties.

[0120] The compounds of the present invention can also be used to conferantistatic properties or microwave-absorbing properties on variousmaterials. The materials concerned are, for example, polymers which takepart in the composition of electronic components, textiles and windows.Homo- or copolymers of the compounds of the invention, which arepreferably non-crosslinked in order to be able to be coated onto thesurface on which the antistatic properties have to be induced, arecompounds suited to this specific use. The comonomer of this type ofapplication makes possible, if appropriate, a good adhesion to thesubstrate to be treated, by the choice of comparable polarities. Inplastics, it is also possible to prepare mixtures with the polymer ofthe invention by techniques known in plastics technology.

[0121] A copolymer obtained by copolymerization of a mixture ofmonofunctional compounds and of difunctional compounds according to thepresent invention is of use in the preparation of membranes. Thehomopolymerization or the copolymerization of the monomers according tothe invention having a perfluorovinyl functional group results in linearpolymers. It is easy, by addition of monomers having more than onepolymerizable functional group, to obtain crosslinked networks. Thesematerials can be used for preparing membranes having an improvedmechanical strength in which the degrees of swelling and the permeationin liquids in which they will be employed can be controlled. Theimprovement in the mechanical strength is also a significant factor inthe preparation of very fine membranes in which the resistance isdecreased and in the reduction of the cost of the starting materials.Likewise, controlling the degree of crosslinking makes it possible toincrease the concentration of attached ions in the membrane withoutinducing excessive solubility or excessive swelling. In processesemploying membranes, it is particularly advantageous to prepare themembrane in its definitive form, in the sheet or pipe form, from aconcentrated solution of monomers in a solvent allowing spreading orextrusion techniques, by copolymerization of the monomers, includingthose which make possible the crosslinking.

[0122] In the preparation of membranes, it is particularly advantageousto use monomer compounds of the present invention which exhibit a highsolubility in the solvents in which the polymerization will be carriedout and a reactivity comparable with that of the double bonds carried bythe monofunctional monomer and of those carried by the polyfunctionalmonomers which make possible the crosslinking, so as to obtain an evendistribution of the crosslinking nodes.

[0123] The membranes obtained from the compounds of the presentinvention can be used in particular in dialysis systems, as separator ina two-phase reactor or for membrane processes of chlorine-sodiumhydroxide type, or for the recovery of effluents, or as electrolyte in afuel cell. As regards fuel cells, a macromolecular material obtainedfrom monomer compounds of the invention can also be used as binder inthe electrode material.

[0124] The monomer compounds of the present invention can be used forthe catalysis of various types of chemical reactions and in particularfor polymerization reactions, condensation reactions, addition orelimination reactions, oxidation or reduction reactions, solvolyses,Friedel-Crafts reactions and Diels-Alder reactions. For theseapplications in catalysis, the monomer compounds will be chosenessentially according to the cation associated with the anionic part.For the catalysis of Diels-Alder reactions or of Friedel-Craftsreactions, alkali metal, alkaline earth metal, transition metal or rareearth metal cations are preferred. It is also possible to use, for theabovementioned catalytic reactions, polymers obtained from theabovementioned monomer compounds. Polyanionic polymers comprising H+,Li⁺, Mg⁺⁺, Ca⁺⁺, Cu⁺⁺, Zn⁺⁺, Al+⁺⁺ or Fe+++cations or rare earth metalcations are preferred. Said polymers are generally put into the powderor granule form. In this case, the separation of the reactants becomesparticularly easy due to the insolubility of the polyanion of theinvention.

[0125] The compounds of the invention in which the cation is an onium ofthe diazonium, sulfonium, iodonium or metallocenium type can be used ascationic polymerization initiator. Under the action of actinicradiation, such compounds generate the corresponding acid form capableof initiating a cationic polymerization reaction. It is also possible touse polymers obtained by polymerization of the abovementioned monomercompounds. The advantages related to the use of polymers are analogousto those of the polymers used in the other abovementioned catalyticreactions. The materials of the invention in the amine salt form can beused as initiator of cationic polymerizations by heating, releasing thecorresponding protonic form. Likewise, if the cation is a salt of acationic azo compound (for example as represented below), it can act, byheating, as initiator of radical polymerizations.

[0126] The present invention is described in more detail by thefollowing examples, the invention not being restricted to theseexamples.

EXAMPLE 1

[0127] An azeotropic distillation of 20 mmol of carboxylic acidCICF₂CFClCOOH and of 10 mmol of hydrazine monohydrate was carried out in200 ml of toluene. After 24 hours, the toluene was evaporated and thecompound ClCF₂CFClCONHNHCOCFClCF₂Cl was obtained. This compound wassubsequently dissolved in 200 ml of PCI₅ comprising 40 mmol ofdimethylaniline hydrochloride. After having brought this mixture toreflux for 24 hours, two phases were obtained after cooling, including adenser CICF₂—CFClCCl═N—N═CCl-CFCl—CF₂CI phase. This product wasrecovered using a separating funnel, washed with water and then treatedwith aqueous ammonia in a mixture of 100 ml of ether and 100 ml of a 4Maqueous ammonia solution. After stirring for 24 hours, the solvents wereevaporated and CICF₂—CFClC(NH₂)═N—N═C(NH₂)CFClCF₂Cl was thus obtained.The latter product was subsequently brought to reflux in 100 ml ofbutanol for 48 hours and then, after the evaporation of butanol, takenup in 100 ml of anhydrous THF comprising zinc. After 24 hours, thesolvent was evaporated and the residual product recrystallized from asaturated KCl solution. After filtration, the recrystallized compoundwas ground up together with ammonium sulfate and then sublimed undervacuum, and the following compound was thus recovered:

EXAMPLE 2

[0128] 10 mmol of hydrazine monohydrate were treated in THF with 15 mmolof CF₃CO₂C₂H₅. After 8 hours, the THF was evaporated and the productdried. CF₃CONHNH₂ was obtained quantitatively. An azeotropicdistillation of this compound with 10 mmol of the carboxylic acidCICF₂CFClCOOH was then carried out in 200 ml of toluene. After 24 hours,the toluene was evaporated and CICF₂CFClCONHNHCOCF₃ was obtained. Thiscompound was subsequently treated by a process analogous to thatdescribed in Example 1 for the compound CICF₂CFClCONHNHCOCFClCF₂CI andthe following compound was obtained:

EXAMPLE 3

[0129] 10 mmol of trifluorovinyl iodide CF₂═CFI were slowly added to 30ml of anhydrous THF at 0° C. under argon comprising 20 mmol of zinc.After stirring for two hours, the excess zinc was removed by filtrationunder argon. 5 mmol of the lithium salt of 2,5-dibromo-1,3,4-triazoleand 1 mmol of Pd[P(C₆H₅)₃]₄ as catalyst were then added to the zincicsolution. After stirring for 24 hours, the solvent was evaporated andthen the residue was ground up together with ammonium hydrogensulfate.After subliming this mixture, the following compound was obtained:

EXAMPLE 4

[0130] 10 mmol of the lithium salt of urazole and 500 mmol of1,8bis(dimethylamino)anthracene were introduced into 50 ml of THF in achemical reactor. After having brought the reaction mixture to −20° C.,20 mmol of tetrafluoroethylene (PCR) were introduced slowly into thereactor. After 24 hours, the reaction mixture was flushed with argon andthen the mixture was allowed to slowly return to room temperature. 30mmol of sodium tert-butoxide, in solution in 20 ml of anhydrous THF,were then slowly added. After 3 hours, the solvent was evaporated andthe residue was recrystallized from a saturated KCl solution and thensublimed, after having been ground up together with ammonium sulfate.The following compound was obtained:

EXAMPLE 5

[0131] 10 mmol of 1-trifluoromethyl-3-hydroxy-2,4,5-triazole werereacted with 10 mmol of tetrafluoroethylene by a process similar to thatdescribed in Example 4. The following compound was thus obtained:

EXAMPLE 6

[0132] 10 mmol of freshly sublimed malononitrile were dissolved in 50 mlof anhydrous THF and then the solution was brought to 0° C. 20 mmol oflithium hydride LiH were then added portionwise. After 2 hours, 10 mmolof CICF₂CFClSO₂F were added. After 48 hours, the solution wascentrifuged in order to remove the LiF precipitate and then the solventwas evaporated.

EXAMPLE 7

[0133] 25.5 g of the acid chloride BrC₆H₄SO₂Cl were suspended in asolution of 5.4 g of ammonium chloride in 100 ml of water maintained at0° C. and then 108 g of 15% sodium hydroxide solution were graduallyadded with vigorous stirring, the addition being controlled so that thepH did not exceed 10.5. The stoichiometric ratio of the reactants was2:1:4. The reaction scheme is: 2 BrC₆H₄SO₂Cl+NH₄Cl+4 NaOH 3 NaCl+(BrC₆H₄SO₂)₂NNa +4H20.

[0134] The solution was subsequently filtered and then evaporated andthe sodium salt of the bis(4-bromobenzenesulfonimide) (BrC₆H₄SO₂)₂NNawas extracted with anhydrous ethanol. The salt was recrystallized from amethanolmethyl ethyl ketone mixture.

EXAMPLE 8

[0135] 24.5 g of 1,1,1,2-tetrafluoroethane were condensed in 300 ml ofanhydrous ether at −78° C. 44 ml of a lOM solution of butyllithium inhexane were subsequently added dropwise with stirring. After one hour,250 ml of a commercial 1M solution of zinc chloride in ether were addedto the reaction mixture. The reaction was carried out according to thefollowing reaction scheme: CF₃CH₂F+C₄H₉Li C₄H, o+CF₂═CFLi +HF CF₂═CFLi+ZnCl₂ CF₂═CFZnCl +LiCl

[0136] The suspension containing the zincic trifluorovinyl was broughtback to ordinary temperature and 45 g of the sodium salt ofbis(bromophenylsulfonimide) (prepared according to the procedure ofExample 7) in 150 ml of anhydrous dimethylformamide were added, as wellas 800 mg of trisbenzylideneacetonedipalladium(0) and 1 g oftriphenylphosphine. The ether was subsequently removed by distillationwhile flushing with dry argon and the mixture was maintained at 70° C.for six hours. The reaction product was filtered and the DMF was removedusing a rotary evaporator under partial vacuum at 60° C. The solidresidue was taken up in 100 ml of water and filtered. Thetetraethylammonium salt of the bis(trifluorovinylphenylsulfonimide) wasprecipitated by addition of 20 g of (C₂H₅)₄NCI in solution in 50 ml ofwater. The crude product was recrystallized from an ethanol-watermixture. It corresponds to the formula:

EXAMPLE 9

[0137] 302 g of iodophenylsulfonyl chloride IC₆H₄SO₂Cl (commercial“pipsyl chloride”) were dissolved in 1 l of acetonitrile at 25° C. and105 g of trifluoromethanesulfonamide and 225 g of1,4-diazabicyclo-[2,2,2]-octane (DABCO) were added. The mixture wasstirred for 8 hours, during which a DABCO hydrochloride precipitate wasformed. The reaction mixture was subsequently filtered and the solventevaporated. The solid residue was taken up in 300 ml of a saturatedpotassium chloride solution and 100 ml of acetic acid. The precipitateformed, which corresponds to the formula:

[0138] was separated by filtration and recrystallized from water.

[0139] 362.6 g of the salt thus prepared were dissolved in 700 ml of DMFand 185 g of the zincic derivative in ether prepared by a processsimilar to that described in Example 8, as well as 2.5 g oftrisbenzilidenedipalladium(0) and 4 g of triphenylphosphine, were added.The ether was subsequently distilled off under an argon flow and themixture was maintained at 60° C. with stirring for 5 hours. The reactionproduct was filtered and the DMF was removed using a rotary evaporatorunder partial vacuum at 60° C. The solid residue was washed with watersaturated with KCl, dried and then washed with dichloromethane. The saltobtained was purified by crystallization from a water-ethanol mixture.It corresponds to the formula:

EXAMPLE 10

[0140] 40 g of the monofunctional ionic monomer prepared according tothe procedure described in Example 9 and 2.9 g of the difunctional ionicmonomer prepared according to the procedure of Example 8 were dissolvedin 100 ml of DMF. 7.5 g of colloidal silica [composed of particleshaving a mean size of 0.007 microns (Aldrich 38,126-8)] and 600 mg of1,2-diphenyl-1-keto-2,2dimethoxyethane

[0141] were added to the solution thus obtained. The suspension washomogenized and degassed by sparging with nitrogen, then sprayed as a 60mm layer over a film of poly(ethylene terephthalate) (PET), and finallysubjected for 50 seconds to UV irradiation of 1 W/cm² produced by a lampof Hanovia type. The film was maintained under a nitrogen blanket duringthe exposure and the postcure of 5 minutes. The viscous solutionsolidified to form an elastic film. The DMF was removed by stoving for48 hours at 80° C., which made it possible to separate thepolyelectrolyte membrane from its PET support. The membrane was washedwith aqueous acidic solution (IM nitric acid solution) renewed severaltimes. The ions (K⁺ TEA) of the membrane thus obtained were exchanged byprotons. The membrane was washed with distilled water and then driedunder vacuum to give a rigid film having a thickness of approximately 18mm and a very good mechanical strength.

EXAMPLE 11

[0142] 4 g of the monofunctional ionic monomer prepared according to theprocedure described in Example 9 and 0.7 g of the difunctional ionicmonomer prepared according to the procedure of Example 8 were dissolvedin 15 ml of DMF and emulsified by vigorous mechanical stirring intoluene, using 500 mg of Brij 35° as surfactant. After degassing, thepolymerization was initiated at 80° C. with 100 mg of benzoyl peroxideand the polymerization was continued for 3 hours at this temperature.The crosslinked suspension of polymer was filtered and then washed withwater and with methanol, so as to remove the DMF. After drying, a fineresin powder was obtained. The cations associated with the sulfonimidegroups were exchanged for yttrium ions by stirring 2 g of the resinobtained in 6 successive baths of 10 ml of IM yttrium chloride. Theresin was dehydrated. It has catalytic properties, in particular in theDiels-Alder and FriedelCrafts reactions, in organic solvents. The use ofthe resin as catalyst is particularly advantageous because of itsinsolubility, which makes possible separation after the reaction bysimple filtration of the reaction mixture.

EXAMPLE 12

[0143] 46.4 g of commercial 4-hydroxybenzenesulfonic acid sodium saltwere dried under vacuum at 60° C. to remove the water of crystallizationand then dissolved in 150 ml of anhydrous ethanol, to which were added14 g of sodium ethoxide and then 28 g of 2-methyl-2-bromopropane. Thesolution was filtered and the solvent evaporated to dryness. The sodium4-t-butoxybenzenesulfonate was recrystallized from a mixture of ethanoland ethyl acetate. 21.4 g of (chloromethylene)dimethylammonium chloride[CH(Cl)═N(CH3)₂]+Cl— were added to 42 g of this salt in suspension in200 ml of anhydrous DMF, the mixture was stirred for 1 hour at 25° C.and then 5.8 g of lithium nitride were added. After reacting for 8hours, the mixture was filtered and the DMF was removed using a rotaryevaporator under partial vacuum at 60° C. The solid residue was taken upin 40 ml of trifluoroacetic acid, which catalyzes the solvolysisreaction of the t-butyl ether. The acid was subsequently distilled offand the mixture was taken up in 80 ml of water with 14 g of potassiumcarbonate. The residue, after evaporation of the water, was extracted inethanol and the following salt was obtained:

[0144] which was recrystallized from this solvent. 22 g of this saltwere suspended in 150 ml of THF in a Parr reactor with 1 g of potassiumt-butoxide. The reactor was purged under argon and tetrafluoroethylenewas introduced under a pressure of 5 bar. After one hour, the pressurefell to 1 atmosphere and the reactor was flushed with argon. The saltobtained, having the formula

[0145] was treated with 13.4 g of potassium t-butoxide in 50 ml ofanhydrous THF. The reaction product was filtered and then evaporated.The monomer salt obtained:

[0146] is recrystallized from water.

EXAMPLE 13

[0147] 18.3 g of the compound

[0148] prepared according to the procedure described in Example 12, wassuspended in 100 ml of anhydrous DMF in a reactor with 2.6 g of sodiumhydride. After cessation of the evolution of hydrogen, 7 g of1,2-dibromotetrafluoroethane were added. The mixture was stirred at 60°C. for 2 hours. The reaction product was subsequently filtered, the DMFevaporated and the residue taken up in water and filtered. The crystalsof

[0149] were dewatered and dried.

[0150] This product was reduced in 150 ml of anhydrous acetonitrile atreflux under argon with 8 g of zinc powder. The resulting solution wasfiltered, in order to remove the excess zinc, and then evaporated. Asalt identical to the preceding example was obtained and recrystallizedfrom an ethanol-water mixture.

[0151] This monomer easily polymerizes by heating, in particular inconcentrated solution, more conveniently in nonvolatile solvents, suchas propylene carbonate, to give, at 150° C., a thermostable linearpolymer:

[0152] In the presence of a monofunctional comonomer, this monomerbehaves as a difunctional monomer, allowing crosslinking.

EXAMPLE 14

[0153] 100 g of ClCF₂CFClSO₂F were synthesized according to the methoddescribed by Forohar Farhad (“Studies of the Chemistry ofPerfluorovinylsulfonyl Fluoride”, Clemson University, Thesis 1990 UMI9115049).

[0154] 10 mmol of freshly sublimed malononitrile were dissolved in 50 mlof anhydrous THF and then the solution was brought to 0° C. 20 mmol oflithium hydride LiH were then added portionwise. After 2 hours, 10 mmolof ClCF₂CFClSO₂F were added. After 48 hours, the solution wascentrifuged to remove the LiF precipitate and then 20 mmol of activatedzinc were added. After stirring for 24 hours, the THF was evaporated andthe residue taken up in acetonitrile and then filtered. Afterevaporation of the filtered solution and drying, the following compoundwas obtained:

EXAMPLE 15

[0155] 10 mmol of trifluorovinyl iodide CF₂═CFI were slowly added to 30ml of anhydrous THF at 0° C. under argon comprising 20 mmol of zinc.After stirring for two hours, the excess zinc was removed by filtrationunder argon. 5 mmol of the potassium salt of bis(chlorosulfonyl)imideand 1 mmol of Pd[P(C₆H₅)₃₁₄, as catalyst, were then added to the zincicsolution. After stirring for 24 hours, the solvent was evaporated andthen the residue was recrystallized from a saturated potassium chloridesolution. After filtering and drying, the following compound wasrecovered: K CF₂═CFSO₂NSO₂CF═CF₂ The lithium salt was obtained by ionicexchange with lithium chloride in tetrahydrofuran.

1. Ionic compound in which the negative charge is highly delocalized,corresponding to the formula [CF₂═CF-A⁻]_(m)M^(m+) in which: M^(m+) is aproton or a metal cation having the valency m chosen from the alkalimetal, alkaline earth metal, transition metal or rare earth metal ionsor an organic onium cation or an organometallic cation, I≦m≦3; A is ananionic group having one of the formulae (I) [—(CF2)_(n)SO₂Z]⁻, (II)[—(O)_(n′)-Φ-SO₂Z]⁻ or (III)

n and n′ represent 0 or 1; Φ represents a condensed or noncondensedaromatic group, which may or may not carry one or more substituents andwhich may or may not comprise heteroatoms, or a polyhalogenated group—C₆H_((4−x−y))F_(x)Cl_(y)-(1≦x+y≦4); Z represents —O or one of the—NC≡N, —C(C≡N)₂, —NSO₂R or C[SO₂R]₂ groups, Z being other than -o when nor n′ are zero; D represents a single bond, an oxygen atom, a sulfuratom, a —CO— carbonyl group or an —SO₂— sulfonyl group; the groups X′ toX⁴, hereinafter denoted by X¹, represent N, C—C≡N, CR, CCOR or CSO₂R, itbeing understood that, in a pentacyclic group, the X¹ groups can beidentical or different; R represents Y, YO—, YS—, Y₂N—, F,R_(F)=C_(q)F2q+1 (preferably 0≦q≦12), CF₂═CF—, CF₂═CFCF₂— or CF₂═CF—O—,it being understood that, if 2 R substituents are present on the samegroup, they can be identical or different; Y represents H or amonovalent organic radical having from 1 to 16 carbon atoms chosen fromalkyl, alkenyl, oxaalkyl, oxaalkenyl, azaalkyl, azaalkenyl, aryl oralkylaryl radicals or from the radicals obtained from the abovementionedradicals by substitution, in the chains and/or the aromatic part, byheteroatoms, such as halogens, oxygen, nitrogen, sulfur or phosphorus,it being understood that, if sulfur or phosphorus are present, they canoptionally be bonded to substituted nitrogen or oxygen atoms, or else Yis a repeat unit of a polymeric backbone.
 2. Compound according to claim1, characterized in that Mm+is a metal cation chosen from the groupconsisting of Li⁺, K⁺, Mg⁺⁺, Ca⁺⁺, Ba⁺⁺, Cu⁺⁺, Zn⁺⁺, Fe++ and Re+++. 3.Compound according to claim 1, characterized in that Mm+is an ammonium[N(Y^(j))₄]+, an amidinium RC[N(Y^(j))₂]₂+, a guanidiniumC[N(Y^(j))₂]₃+, a pyridinium [C₅N(Y^(j))₆]+, an imidazoliumC₃N₂(Y^(j))₅+, an imidazolinium C₃N₂(Y^(j))₇+, a triazoliumC₂N₃(Y^(j))₄+, a carbonium C₅(Y^(j))_(n)C+, an NO+(nitrosyl), NO₂+, asulfonium [S(Y^(j))₃]+, a phosphonium [P(Y^(j))₄]+or an iodonium[I(Y^(j))₂]+, the Yi substituents of the same cation, which can beidentical or different, representing one of the substituents indicatedfor Y.
 4. Compound according to claim 1, characterized in that M^(m+) isan organometallic cation chosen from metalloceniums; metal cationscoordinated by atoms, such as O, S, Se, N, P or As, carried by organicmolecules, these cations optionally forming part of a polymericbackbone; or a trialkylsilyl, trialkylgermanyl or trialkylstannyl group.5. Compound according to claim 1, characterized in that the M+cation isthe repeat unit of a conjugated polymer in cationic oxidized form. 6.Compound according to claim 1, characterized in that the divalentradical Φ is a phenyl C₆H₄ corresponding to the ortho, meta and parapositions of substitution or an aromatic group, a phenyl which issubstituted and/or comprising condensed nuclei which may or may notcomprise heteroatoms.
 7. Compound according to claim 1 corresponding toone of the following formulae: {[CF₂═CF—SO₂NCN]⁻}_(m)M^(m+),{[CF₂═CF—SO₂C(CN)₂]⁻}_(m)M^(m+), {[CF₂═CFCF₂—SO₂NCN]⁻}_(m)M^(m+),{[CF₂═CFCF₂—SO₂C(CN)₂]⁻}_(m)M^(m+), {[CF₂═CFΦSO₂NCN]⁻}_(m)M^(m+),{[CF₂═CF-ΦSO₂C(CN)₂]1}_(m)M^(m+), {[CF₂═CFΦSO₂NSO₂CF₃]⁻}_(m)M^(m+),{[CF₂═CF-Φ)SO₂C(SO₂CF₃)₂]⁻}_(m)M^(m+),{[CF₂═CF-ΦSO₂CH(SO₂CF₃)]⁻}_(m)M^(m+),


8. Compound according to claim 1 corresponding to one of the followingformulae: {[(CF₂═CF—SO₂)₂N]⁻}_(m)M^(m+),{[(CF₂═CFCF₂—SO₂)₂N]⁻}_(m)M^(m+), {[(CF₂═CFSO₂)₂CH]⁻}_(m)M^(m+),{[(CF₂═CFCF₂—SO₂)₂CH]⁻}_(m)M^(m+), {[(CF₂═CFSO₂)₃C])}_(m)M^(m+),{[(CF₂═CFCF₂—SO₂)₃C]⁻}_(m)M^(m+), {[(CF₂═CF-ΦSO₂)₂N]⁻}_(m)M^(m+),{[(CF₂═CF—O-ΦSO₂)₂N]⁻}_(m)M^(m+), {[(CF₂═CF-ΦSO₂)₂CH]⁻}_(m)M^(m+),{[(CF₂═CF—OΦSO₂)₂CH]⁻}_(m)M^(m+), {[(CF₂═CF-ΦSO₂)₃C]⁻}_(m)M^(m+),{[(CF₂═CF—O-ΦSO₂)₂CH]⁻}_(m)M^(m+), {[(CF₂═CF-ΦSO₂)₃C]⁻}_(m)M^(m+),{[(CF₂═CF-O-ΦSO₂)₃C]}_(m)M^(m+), {[(CF₂═CF—)₂C₆H₃SO₃]}_(m)M^(m+),{[3,5-(CF₂═CF—)₂C₆H₃SO₂NSO₂CF₃]⁻}Mm+


9. Process for the preparation of an ionic compound according to claim1, in which an organometallic compound (OM1) is reacted instoichiometric proportions with an ionic compound (IC1) in the presenceof a catalyst, characterized in that: the organometallic compound (OMI)corresponds to the formula [CF₂═CF—(CF₂)_(n)]e-E, in which: E representsLi, MgL¹, ZnL¹, CdL¹, Cu, Mg, Zn, Cd, Hg or a trialkylsilyl,trialkylgermanyl or trialkylstannyl group; n is 0 or 1; e represents thevalency of E; L¹ represents a leaving group chosen from halogens,pseudohalogens, sulfonates, radicals comprising imidazole or1,2,4-triazole rings and their homologs in which one or more carbonatoms carry substituents, including those in which the substituents forma ring, perfluoroalkylsulfonyloxy radicals and arylsulfonyloxy radicals;the ionic compound (IC1) corresponds to the formula [(LA¹)]_(m′)M′_(m′+)in which: M^(m+) represents a proton or a metal cation having thevalency m chosen from ions of alkali metals, of alkaline earth metals,of transition metals or of rare earth metals or an organic onium cationor an organometallic cation, 1≦m≦3, M′ being chosen so as not tointerfere with the formation reaction; L has the same meaning as L′, itbeing understood that the L and L′ groups of the respective reactantsused during a reaction can be identical or different; A′ represents ananionic group corresponding to one of the following formulae[—(CF₂)_(n)—SO₂Z′]⁻, [—(O)ΦSO₂Z′] or

in which: n and n′ represent 0 or 1; D represents a single bond, anoxygen atom, a sulfur atom, a —CO— carbonyl group or an —SO₂— sulfonylgroup; Z′ represents the —O oxygen (except if n or n′ are zero) or oneof the —NC—N, —C(C═N)₂, —NSO₂R′ and —C[SO₂R′]₂ groups; the X″ to X′⁴groups, hereinafter denoted by X′¹, represent N, CC—N, CR′, CCOR′ orCSO₂R′, it being understood that, in a pentacyclic group, the X” groupscan be identical or different; R¹ represents Y, YO—, YS—, Y₂N—, F,CF₂═CF—, CF₂═CFCF₂—, CF₂═CF—O— or R_(F)=C_(q)F₂q+, (0≦q≦12), or aleaving group chosen from halogens, pseudohalogens, sulfonates, radicalscomprising imidazole or 1,2,4triazole rings and their homologs,perfluoroalkylsufonyloxy radicals and arylsulfonyloxy radicals, it beingunderstood that, if two R′ substituents are present on the same group,they can be identical or different and that at most two R1 substituentsare leaving groups; —Y has the meaning given in claim
 1. 10. Processaccording to claim 9, characterized in that the M′ cation is replaced bythe M cation by cation exchange.
 11. Process according to claim 9,characterized in that the catalyst is chosen from derivatives of nickelor palladium coordinated with bases of amine or phosphine type. 12.Process according to claim 11, characterized in that the catalyst ischosen from nickel bis(2,2′-bipyridyl), nickeltetrakis(triphenylphosphine) and its sulfonated derivatives, palladiumacetate, trisbenzylideneketonedipalladium, palladiumtetrakis(triphenylphosphine) and its sulfonated derivatives, and thecompounds obtained by replacement of two triphenylphosphine molecules by[(C₆H₅)₂PCH₂]₂ or [(C₆H₅)₂PCH₂]₂CH₂.
 13. Process for the preparation ofan ionic compound [CF₂═CF-A⁻]mMm+according to claim 1, characterized inthat a compound comprising a protected fluorovinyl groupCF₂L³CFL⁴-(CF₂)_(n)E′ is reacted in stoichiometric proportions with areactant [(L⁵)_(a)A²]_(m′)M′^(m′+) making possible the formation of theanionic group A and then the protective groups are removed by a chemicalor electrochemical reduction or by a dehydrohalogenation, and in that:M^(m′+) is a proton or a metal cation having the valency m chosen fromalkali metal, alkaline earth metal, transition metal or rare earth metalions or an organic onium cation or an organometallic cation, 1≦m≦3,M′^(m′+) being chosen so as not to interfere with the formationreaction; L³ and L⁴ represent H or a halogen, just one among themoptionally being H; E′ represents Li, MgL′, ZnL′, CdL′, Cu, Mg, Zn, Cd,Hg or a trialkylsilyl, trialkylgermanyl or trialkylstannyl group; L⁵represents a leaving group chosen from halogens, pseudohalogens,sulfonates, radicals comprising imidazole or 1,2,4-triazole rings andtheir homologs in which one or more carbon atoms carry substituents,including those in which the substituents form a ring,perfluoroalkylsulfonyloxy radicals and arylsulfonyloxy radicals; a isthe valency of the anionic group A 2; A² is an anionic groupcorresponding to one of the following formulae [—(CF₂)_(n)—SO₂Z²]⁻,[—(O)ΦSO₂Z²]- or

in which: Z² represents the -o oxygen (except if n or n′ are zero) orone of the groups —NC≡N, —C(C≡N)₂, —NSO₂R² or —C[SO₂R²]₂; the groups X′¹to X′⁴, hereinafter denoted by X′¹, represent N, CC═N, CR², CCOR² orCSO₂R², it being understood that, in a pentacyclic group, the X′¹ groupscan be identical or different; R² represents —OH, —SH, Y, YO—, YS—,Y₂N—, F, CF₂═CF—, CF₂═CFCF₂—CF₂═CF—O— or R_(F)=C_(q)F2q+(0≦q≦12), itbeing understood that, if two R² substituents are present on the samegroup, they can be identical or different and that at most two R²substituents represent —OH or —SH .
 14. Process according to claim 13,characterized in that the groups L³L⁴ are removed by reduction using areducing agent chosen from zinc, the copperzinc couple, Ti³+, V²+, Cr³⁺or Sm²+salts, and tetrakis- (dimethylaminoethylene) {[(CH₃)₂N]₂C=12. 15.Process for the preparation of a compound according to claim 1,characterized in that a compound CF₂═CFL², in which L² represents Cl, Bror F, is reacted in stoichiometric proportions with an ionic compound[(HQA 3)]_(m′)M′^(m′+), and in that the addition product obtained istreated with a strong base B; (M′^(m′+) represents a proton or a metalcation having the valency m chosen from alkali metal, alkaline earthmetal, transition metal or rare earth metal ions or an organic oniumcation or an organometallic cation, 1≦m≦3, M′^(m+) being chosen so asnot to interfere with the formation reaction; Q represents O or S; A³represents an anionic group corresponding to one of the followingformulae [—(CF₂)_(n)—SO₂Z³]⁻, [-ΦSO₂Z³]⁻ or

in which: Z³ represents the —O oxygen (except if n is zero) or one ofthe groups —NC≡N, —C(C≡N)₂, —NSO₂R³ or —C[SO₂R³]₂; the groups X″″ toX″′⁴, hereinafter denoted by X′¹, represent N, CC—N, CR³, CCOR³ orCSO₂R³, it being understood that, in a pentacyclic group, the X′¹ groupscan be identical or different; —R³ represents HO—, HS—, Y, YO—, YS—,Y₂N—, F, CF₂═CF—, CF₂═CFCF₂—CF≡CF—O— or R_(F)=C_(q)F2q+, (0≦q≦12), itbeing understood that, if two R³ substituents are present on the samegroup, they can be identical or different and that at most two R³substituents are —OH or —SH groups.
 16. Process according to claim 15,characterized in that the strong base B is NaH (optionally used in thepresence of phosphorus-comprising bases of phosphazene type),(CH₃)₃CONa, (CH₃)₃COK, LDA (lithium diisopropylamide), [(CH₃)₂CH]₂NLi,or a hexaalkyldisilazane derivative.
 17. Process for the preparation ofa compound according to claim 1, characterized in that a compoundL⁶CF₂CF₂L⁶ is reacted in stoichiometric proportions with an ioniccompound [(HQA³)⁻]_(m)M′^(m′+) and in that the substitution product issubjected to a chemical or electrochemical reduction, and in that;(M′)^(m′+) represents a proton or a metal cation having the valency mchosen from alkali metal, alkaline earth metal, transition metal or rareearth metal ions or an organic onium cation or an organometallic cation,1≦m≦3, M′^(m+) being chosen so as not to interfere with the formationreaction; Q represents O or S; A³ represents an anionic groupcorresponding to one of the following formulae [—(CF₂)_(n)—SO₂Z³]⁻,[-ΦSO₂Z³]⁻ or

in which: Z³ represents the -o oxygen (except if n is zero) or one ofthe groups —NC≡N, —C(C≡N)₂, —NSO₂R³ or —C[SO₂R³]₂; the groups X″¹ toX″′⁴, hereinafter denoted by X″″, represent N, C—C≡N, CR³, CCOR³ orCSO₂R³, it being understood that, in a pentacyclic group, the X groupscan be identical or different; —R³ represents HO—, HS—, Y, YO—, YS—,Y₂N—, F, CF₂═CF—, CF₂═CFCF₂—CF═CF—O— or R_(F)=C_(q)F2q+1 (0≦q≦12), itbeing understood that, if two R³ substituents are present on the samegroup, they can be identical or different and that at most two R³substituents are —OH or —SH groups; L⁶ represents a halogen, apseudohalogen or a sulfonate.
 18. Process according to claim 17,characterized in that use is made of a catalyst chosen from zinc, thecopper-zinc couple, Ti³+, V²+, Cr³⁺ or Sm²⁺ salts andtetrakis(dimethylaminoethylene) {[(CH₃)₂N]₂C=}2 in carrying out thereduction.
 19. Polymer composed of a polyanionic part with which areassociated cations in a sufficient number to ensure the electronicneutrality of the polymer, characterized in that the polyanionic partcomprises repeat units:

in which A has the meaning indicated in claim
 1. 20. Polymer composed ofa polyanionic part with which are associated cations in a numbersufficient to ensure the electronic neutrality of the polymer,characterized in that the polyanionic part comprises repeat unitscorresponding to the formula:

in which A′⁻ represents an anion corresponding to one of the formulae(I), (II) or (III) defined in claim 1 in which a Z or Xi substituentcomprises a perfluorovinyl radical.
 21. Crosslinked macromolecularmaterial obtained by polymerization or copolymerization of a compoundaccording to claim 1 carrying at least two CF₂═CF— groups.
 22. Tonicallyconducting material composed essentially of a polymer according to claim19.
 23. Electrolyte composed of a solution of a compound according toclaim 1 in a polar solvent.
 24. Electrolyte composed of at least onepolar solvent and a polymer or copolymer obtained by polymerization of amonofunctional compound according to claim
 1. 25. Solid electrolyte,characterized in that it comprises a copolymer of at least one compoundaccording to claim 1 and of one or more precursors of solvatingpolyethers.
 26. Solid electrolyte, characterized in that it comprises amacromolecular material obtained by co-crosslinking of at least onecompound according to claim 1 and of a solvating polyether carryingreactive functional groups capable of reacting with the perfluorovinylgroup of said compound.
 27. Solid electrolyte, characterized in that itcomprises a mixture of a polyether and of a homopolymer or of acopolymer obtained from at least one compound according to claim 1, itbeing possible for said mixture optionally to be crosslinked in order toform an interpenetrating network.
 28. Solid electrolyte, characterizedin that it comprises either a copolymer of at least one compoundaccording to claim 1 and of one or more precursors of solvatingpolyethers or a macromolecular material obtained by co-crosslinking ofat least one compound according to claim 1 and of a solvating polyethercarrying reactive functional groups capable of reacting with theperfluorovinyl group of the compounds of the invention.
 29. Plasticizedelectrolyte or electrolyte in gel form, characterized in that it iscomposed of a mixture of at least one polar solvent, of an ionic monomercompound according to claim 1 and of a polar polymer or of at least onepolar solvent and a polymer or copolymer obtained by polymerization of amonofunctional compound according to claim
 1. 30. Electrolyte accordingto claim 23, characterized in that the cation of the compound accordingto claim 1 is an alkali metal cation.
 31. Primary or secondary batterycomprising a negative electrode, a positive electrode and anelectrolyte, characterized in that the electrolyte comprises an ioniccompound according to claim 1 or a macromolecular material obtained froman ionic compound according to claim
 1. 32. Primary or secondary batterycomprising a negative electrode, a positive electrode and anelectrolyte, characterized in that the electrolyte is an electrolyteaccording to one of claim
 23. 33. System for modulating light comprisingan electrolyte and electrodes, characterized in that the electrolytecomprises an ionic compound according to claim 1 or a macromolecularmaterial obtained from an ionic compound according to claim
 1. 34.Supercapacitor composed of an electrolyte and electrodes, characterizedin that the electrolyte comprises an ionic compound according to claim 1or a macromolecular material obtained from an ionic compound accordingto claim
 1. 35. Process for doping a polymer which consists in partiallyoxidizing said polymer in order to create carbocations, the charge ofwhich is compensated for by the anions of an ionic compound,characterized in that the ionic compound is a compound according toclaim
 1. 36. Process for doping a polymer according to claim 35,characterized in that the ionic compound is chosen from those in which Zis —C(C≡N)₂, —NSO₂R or —C(SO₂R)₂.
 37. Process for the polymerization orcrosslinking of monomers or prepolymers capable of reacting by thecationic route, characterized in that use is made of a compoundaccording to claim 1 as photoinitiator which is the source of acidcatalyzing the reaction.
 38. Use of an ionic polymer according to claim19 as catalyst for polymerization reactions, condensation reactions,addition or elimination reactions, oxidation or reduction reactions,solvolyses, Friedel-Crafts reactions and Diels-Alder reactions. 39.Ionically conducting material comprised essentially of a polymeraccording to claim
 20. 40. Tonically conducting material comprisedessentially of a crosslinked macromolecular material according to claim21.
 41. Electrolyte according to claim 25, characterized in that thecation of the compound is an alkali metal cation.
 42. Electrolyteaccording to claim 26, characterized in that the cation of the compoundis an alkali metal cation.
 43. Primary or secondary battery comprising anegative electrode, a positive electrode and an electrolyte,characterized in that the electrolyte is an electrolyte according toclaim
 25. 44. Primary or secondary battery comprising a negativeelectrode, a positive electrode and an electrolyte, characterized inthat the electrolyte is an electrolyte according to claim
 26. 45. Use ofan ionic polymer according to claim 20 as catalyst for polymerizationreactions, condensation reactions, addition or elimination reactions,oxidation or reduction reactions, solvolyses, Friedel-Craft reactionsand Diels-Alder reactions.
 46. A dialysis system or a two-phase reactoror a fuel cell containing a membrane comprised of a crosslinkedcopolymer of at least two ionic compounds in which the negative chargeis highly delocalized, corresponding to the formula[CF₂═CF-A⁻]_(m)M^(m+) in which: Mm+is a proton or a metal cation havingthe valency m chosen from the alkali metal, alkaline earth metal,transition metal or rare earth metal ions or an organic onium cation oran organometallic cation, 1 m 3; A is an anionic group having one of theformulae (I) [—(CF₂)_(n)SO₂Z]⁻, (II) [—(O)ΦSO₂Z]⁻ or (III)

n and n′ represent 0 or 1; Φ represents a condensed or noncondensedaromatic group, which may or may not carry one or more substituents andwhich may or may not comprise heteroatoms, or a polyharlongenated group—C₆H(₄xy)FxC1y- (1≦x+y≦4); Z represents -0 or one of the —NC≡N,—C(C≡N)₂, —NSO₂R or C[SO₂R]₂ groups, Z being other than -o when n or n′are zero; D represents a single bond, an oxygen atom, a sulfur atom, a—CO— carbonyl group or an —SO₂— sulfonyl group; the groups X′ to X⁴′,hereinafter denoted by X′, represent N, CC—N, CR, CCOR or CSO₂R, itbeing understood that, in a pentacyclic group, the X¹ groups can beidentical or different; R represents Y, YO—, YS—, Y₂N—, F,R_(F)=C_(q)F2q+, (preferably 0≦q≦12), CF₂═CF—, CF₂═CFCF₂— or CF₂═CF—O—,it being understood that, if 2 R substituents are present on the samegroup, they can be identical or different; Y represents H or amonovalent organic radical having from 1 to 16 carbon atoms chosen fromalkyl, alkenyl, oxaalkyl, oxaalkenyl, azaalkyl, azaalkenyl, aryl oralkylaryl radicals or from the radicals obtained from the abovementionedradicals by substitution, in the chains and/or the aromatic part, byheteroatoms, such as halogens, oxygen, nitrogen, sulfur or phosphorus,it being understood that, if sulfur or phosphorus are present, they canoptionally be bonded to substituted nitrogen or oxygen atoms, or else Yis a repeat unit of a polymeric backbone; and at least one of the ioniccompounds carries only one CF₂═CF-group and at least one of the ioniccompounds carries at least two CF₂═CF-groups.